TY - JOUR
T1 - Multiconfiguration Pair-Density Functional Theory for Chromium(IV) Molecular Qubits
AU - Sauza-De La Vega, Arturo
AU - Pandharkar, Riddhish
AU - Stroscio, Gautam D.
AU - Sarkar, Arup
AU - Truhlar, Donald G.
AU - Gagliardi, Laura
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/9/26
Y1 - 2022/9/26
N2 - Pseudotetrahedral organometallic complexes containing chromium(IV) and aryl ligands have been experimentally identified as promising molecular qubit candidates. Here we present a computational protocol based on multiconfiguration pair-density functional theory for computing singlet-triplet gaps and zero-field splitting (ZFS) parameters in Cr(IV) aryl complexes. We find that two multireference methods, multistate complete active space second-order perturbation theory (MS-CASPT2) and hybrid multistate pair-density functional theory (HMS-PDFT), perform better than Kohn-Sham density functional theory for singlet-triplet gaps. Despite the very small values of the ZFS parameters, both multireference methods performed qualitatively well. MS-CASPT2 and HMS-PDFT performed particularly well for predicting the trend in the ratio of the rhombic and axial ZFS parameters, |E/D|. We have also investigated the dependence and sensitivity of the calculated ZFS parameters on the active space and the molecular geometry. The methodologies outlined here can guide future prediction of ZFS parameters in molecular qubit candidates.
AB - Pseudotetrahedral organometallic complexes containing chromium(IV) and aryl ligands have been experimentally identified as promising molecular qubit candidates. Here we present a computational protocol based on multiconfiguration pair-density functional theory for computing singlet-triplet gaps and zero-field splitting (ZFS) parameters in Cr(IV) aryl complexes. We find that two multireference methods, multistate complete active space second-order perturbation theory (MS-CASPT2) and hybrid multistate pair-density functional theory (HMS-PDFT), perform better than Kohn-Sham density functional theory for singlet-triplet gaps. Despite the very small values of the ZFS parameters, both multireference methods performed qualitatively well. MS-CASPT2 and HMS-PDFT performed particularly well for predicting the trend in the ratio of the rhombic and axial ZFS parameters, |E/D|. We have also investigated the dependence and sensitivity of the calculated ZFS parameters on the active space and the molecular geometry. The methodologies outlined here can guide future prediction of ZFS parameters in molecular qubit candidates.
KW - Chromium(IV) aryl complexes
KW - Molecular qubits
KW - Multiconfigurational calculations
KW - Optically addressable qubits
KW - Singlet-triplet gap
KW - Zero-field splitting
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U2 - 10.1021/jacsau.2c00306
DO - 10.1021/jacsau.2c00306
M3 - Article
C2 - 36186551
AN - SCOPUS:85137881087
SN - 2691-3704
VL - 2
SP - 2029
EP - 2037
JO - JACS Au
JF - JACS Au
IS - 9
ER -